Vetiver odorant

ABSTRACT

Compounds of formula (I) in the form of any one of its stereoisomers or a mixture thereof are provided, wherein the dotted lines represent a carbon-carbon single bond or a carbon-carbon double bond; and one R 1  group represents a hydrogen atom and the second R 1  group represents a methyl group. Also provided are their uses as perfuming ingredients to impart vetiver/rooty and powdery notes; e.g. in perfuming compositions or in consumer products.

TECHNICAL FIELD

The present invention relates to the field of perfumery. Moreparticularly, it concerns the compound of formula (I) as defined hereinbelow, and their uses as perfuming ingredients, e.g. in perfumingcompositions and/or consumer products.

PRIOR ART

The perfumery industry is constantly on the lookout for new ingredientsin order to support the creativity of perfumer by diversifying the notespresent in their palette. One of the key organoleptic families inperfumery is the woody note which is very important in perfumerycreation.

The present invention provides a new compound belonging to this family.Actually, the compound of formula (I) as reported in the presentinvention imparts a very interesting woody note.

To the best of our knowledge the compound of formula (I) is novel andthe only related analogue reported in the literature, and described forits odor properties, is1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone,i.e. a derivative having a syn configuration between the two methylgroups at carbon 4a and 8 (see N. Baldovini et al, in Flavour Frag. J.,2015, 30, 26). Said prior art analogue has been defined in nature anddescribed has having a woody-fruity damascone odor, i.e. significantlydifferent from the any one of the present compounds.

The prior art document does not report or suggest any organolepticproperties of the compound of formula (I), or any use of said compoundin the field of perfumery.

SUMMARY OF THE INVENTION

The invention relates to compound of formula (I) which imparts an odorof woody/rooty and powdery type which is very appreciated in perfumery.

So, a first object of the present invention is a use of a compound offormula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, wherein the dotted lines represent a carbon-carbon        single bond or a carbon-carbon a double bond; and one R¹ group        represents a hydrogen atom and the second R¹ group represents a        methyl group.

A second object of the invention is a compound of formula (I) as definedabove.

A third object of the invention is a perfuming composition comprising

i) at least one compound of formula (I), as defined above;ii) at least one ingredient selected from the group consisting of aperfumery carrier and a perfumery base; andiii) optionally at least one perfumery adjuvant.

Another object of the invention is a perfumed consumer productcomprising at least one compound of formula (I) as defined above or aperfuming composition as defined above.

A last object of the invention is a method to confer, enhance, improveor modify the odor properties of a perfuming composition or of aperfumed article, which method comprises adding to said composition orarticle an effective amount of at least a compound of formula (I) asdefined above.

DESCRIPTION OF THE INVENTION

We have now surprisingly discovered a compound of formula (I) impartinga very powerful woody type note.

So the first object of the present invention is a use of a compound offormula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, wherein the dotted lines represent a carbon-carbon        single bond or a carbon-carbon double bond; and one R¹ group        represents a hydrogen atom and the second R¹ group represents a        methyl group.

Said compounds can be used as perfuming ingredient, for instance toimpart a powerful odor notes of the woody type in the direction ofvetiver/rooty type and surprisingly also of the powdery type.

For the sake of clarity, by the expression “any one of its stereoisomersor a mixture thereof”, or the similar, it is meant the normal meaningunderstood by a person skilled in the art, i.e. that the invention'scompound can be a pure enantiomer or diastereomer (e.g. the hydrogenatom on the carbon 8a in a syn or anti conformation relative to themethyl group in position 4a and carbon 5 or 7 bearing a methyl group ina syn conformation relative to the methyl group in position 4a). Inother words, the invention's compound possesses up to 5 stereocenters,preferably 4 stereocenters, i.e. carbon 2, 4a, 8, 8a and 5 or 7,preferably carbon 4a, 8, 8a and 5 or 7. Each of said stereocenter canhave two different stereochemistries (e.g. R or S). The compound mayeven be in the form of a pure enantiomer or in the form of a mixture ofenantiomers or diastereoisomers. The invention's compound can be in aracemic form or scalemic form. Therefore the compound of formula (I) canbe one stereoisomers or in the form of a composition of mattercomprising, or consisting of, various stereoisomers. Preferably, the twomethyl groups at carbon 4a and 8 are in an anti-configuration eitherrelative or absolute.

For the sake of clarity, by the expression “the dotted lines represent acarbon-carbon single bond or a carbon-carbon double bond”, or thesimilar, it is meant the normal meaning understood by a person skilledin the art, i.e. that the whole bonding (solid and dotted line) betweenthe carbon atoms connected by said dotted line, e.g. carbon 1 and 2, isa carbon-carbon single or double bond; provided that two adjoiningdotted lines are not both double bonds; i.e. when the bond betweencarbon 1 and carbon 2 is a double bond, the bond between carbon 2 andcarbon 3 will be a single bond.

According to any one of the above embodiments of the invention, at mosttwo non-adjoining dotted lines represent a carbon-carbon double bond andthe others a carbon-carbon single bond

According to any one of the above embodiments of the invention, compound(I) can be a compound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, and wherein at least one dotted line represents a        carbon-carbon single bond and the others a carbon-carbon double        bond; and one R¹ group represents a hydrogen atom and the second        R¹ group represents a methyl group. Preferably, two dotted lines        represent a carbon-carbon single bond and the other a        carbon-carbon double bond.

According to a particular embodiment of the invention, compound (I) canbe a compound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof.

According to any one of the above embodiments of the invention, compound(I) can be a compound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, and wherein one dotted line represents a carbon-carbon        single bond and the other a carbon-carbon double bond; and one        R¹ group represents a hydrogen atom and the second R¹ group        represents a methyl group.

According to any one of the above embodiments of the invention, compound(I) can be a compound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, and wherein the bold and hatched lines indicate a        relative or absolute configuration; one dotted line represents a        carbon-carbon single bond and the other a carbon-carbon double        bond; and one R¹ group represents a hydrogen atom and the second        R¹ group represents a methyl group.

For the sake of clarity, by the expression “the bold and hatched linesindicate a relative or absolute configuration” or the similar, it ismeant the normal meaning understood by a person skilled in the art, i.e.that in the case of an relative configuration compound (I) is in theform of a mixture of stereoisomers comprising more than 50% (w/w) of the(4aRS,8RS) stereoisomer when carbon 7 bears R¹ being a methyl group,i.e. a compound having the two methyl groups in a relative transconfiguration as shown in formula (I), or in the case of an absoluteconfiguration compound (I) is in the form of a mixture of stereoisomerscomprising more than 50% (w/w) of the (4aS,8S) stereoisomer when carbon7 bears R¹ being a methyl group.

For the sake of clarity, by the expression “(4aRS,8RS)” it is meant anequimolar mixture of (4aR,8R) and (4aS,8S).

According to a particular embodiment of the invention, said compound(VI) is a compound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, and wherein the bold and hatched lines indicate a        relative or absolute configuration; and one dotted line        represents a carbon-carbon single bond and the other a        carbon-carbon double bond.

According to a particular embodiment of the invention, compound (VI) maybe1-((4aRS,8RS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,8RS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneor a mixture thereof. More particularly, compound (VI) may be1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneor a mixture thereof.

According to any embodiment of the invention, said compound (V) is acompound of formula

-   -   in the form of any one of its stereoisomers or a mixture        thereof, and wherein the bold and hatched lines indicate a        relative or absolute configuration; and one dotted line        represents a carbon-carbon single bond and the other a        carbon-carbon double bond.

According to a particular embodiment of the invention, compound (VII)may be1-((4aSR,8RS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,8RS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneor a mixture thereof. More particularly compound (VII) may be1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneor a mixture thereof.

In the present invention the term “compound of formula (I)” isconstructed in order to encompass also all composition of matterresulting from the admixture of at least two chemicals responding toformula (I). In particular, said compound of formula (I) can be in theform of a composition of matter comprising compound (III), compound (VI)and compound (VII). As non-limiting example, compound of formula (I) canbe in the form of a composition of matter comprising, or consisting of:

-   1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one;-   1-((4aSR,8SR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one;-   1-((4aSR,8SR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one;-   1-((4aRS,8SR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one;    and-   1-((4aRS,8SR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one.

As specific examples of the invention's compounds, one may cite, asnon-limiting example, a mixture of1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,8RS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,8RS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,8RS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-((4aSR,8RS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-onewhich has a very good woody odor in the direction of vetiver/rooty typein addition to a smoky odor and accompanied to an amber, powdery andviolet character. The powdery/iris character of this ingredient isreminiscent of Myrrhone®(4-(2,2,C-3,T-6-tetramethyl-R-1-cyclohexyl)-3-buten-2-one, trademark andorigin: Firmenich SA). This mixture is also very powerful.

As non-limiting, examples of the invention's compounds, one may cite thefollowing ones in Table 1:

TABLE 1 Invention's compounds structures and their odor propertiesCompound structure and name Odor notes

See above: vetiver/rooty, smoky, and powdery odor very powerful

Prior art compound

Grapefruit- rhubarb, woody-fruity, damascone like odor

According to a particular embodiment of the invention, the compound offormula (I) is1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand/or mixtures thereof.

When the odor of the invention's compounds is compared with that of theprior art compound1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone(i.e. the cis compound), then the invention's compounds distinguishthemselves by being largely more powerful and by having apowdery/violet/iris character in addition to the woody note.

Furthermore, the woody note associated with the invention's compounds isof the rooty type, i.e. a warm heavy effect, while the woody noteassociated with the prior art compounds is of the cedar type, i.e. aresin, sawdust, fresh effect. The odor of the invention's compoundsdistinguish also from the prior art by lacking, or not possessingsignificant, fruity notes and damsacone notes, which are characteristicof the prior art compound. Said differences, besides being notforeseeable, lend the invention's compounds and the prior art compoundto be each suitable for different uses, i.e. to impart differentorganoleptic impressions.

As mentioned above, the invention concerns the use of a compound offormula (I) as perfuming ingredient. In other words, it concerns amethod or a process to confer, enhance, improve or modify the odorproperties of a perfuming composition or of a perfumed article or of asurface, which method comprises adding to said composition or article aneffective amount of at least a compound of formula (I), e.g. to impartits typical note.

By “use of a compound of formula (I)” it has to be understood here alsothe use of any composition containing a compound (I) and which can beadvantageously employed in the perfumery industry.

Said compositions, which in fact can be advantageously employed asperfuming ingredients, are also an object of the present invention.

Therefore, another object of the present invention is a perfumingcomposition comprising:

i) as a perfuming ingredient, at least one invention's compound asdefined above;ii) at least one ingredient selected from the group consisting of aperfumery carrier and a perfumery base; andiii) optionally at least one perfumery adjuvant.

By “perfumery carrier” it is meant here a material which is practicallyneutral from a perfumery point of view, i.e. that does not significantlyalter the organoleptic properties of perfuming ingredients. Said carriermay be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifyingsystem, i.e. a solvent and a surfactant system, or a solvent commonlyused in perfumery. A detailed description of the nature and type ofsolvents commonly used in perfumery cannot be exhaustive. However, onecan cite as non-limiting examples, solvents such as butylene orpropylene glycol, glycerol, dipropyleneglycol and its monoether,1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropylmyristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethano,tri-ethyl citrate or mixtures thereof, which are the most commonly used.For the compositions which comprise both a perfumery carrier and aperfumery base, other suitable perfumery carriers than those previouslyspecified, can be also ethanol, water/ethanol mixtures, limonene orother terpenes, isoparaffins such as those known under the trademarkIsopar® (origin: Exxon Chemical) or glycol ethers and glycol etheresters such as those known under the trademark Dowanol® (origin: DowChemical Company), or hydrogenated castors oils such as those knownunder the trademark Cremophor® RH 40 (origin: BASF).

Solid carrier is meant to designate a material to which the perfumingcomposition or some element of the perfuming composition can bechemically or physically bound. In general such solid carriers areemployed either to stabilize the composition, or to control the rate ofevaporation of the compositions or of some ingredients. The use of solidcarrier is of current use in the art and a person skilled in the artknows how to reach the desired effect. However by way of non-limitingexample of solid carriers, one may cite absorbing gums or polymers orinorganic material, such as porous polymers, cyclodextrins, wood basedmaterials, organic or inorganic gels, clays, gypsum talc or zeolites.

As other non-limiting examples of solid carriers, one may citeencapsulating materials. Examples of such materials may comprisewall-forming and plasticizing materials, such as mono, di- ortrisaccharides, natural or modified starches, hydrocolloids, cellulosederivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins,or yet the materials cited in reference texts such as H. Scherz,Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel inLebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie,Lebensmittelqualitat, Behr's Verlag GmbH & Co., Hamburg, 1996. Theencapsulation is a well-known process to a person skilled in the art,and may be performed, for instance, by using techniques such asspray-drying, agglomeration or yet extrusion; or consists of a coatingencapsulation, including coacervation and complex coacervationtechnique.

As non-limiting examples of solid carriers, one may cite in particularthe core-shell capsules with resins of aminoplast, polyamide, polyester,polyurea or polyurethane type or a mixture thereof (all of said resinsare well known to a person skilled in the art) using techniques likephase separation process induced by polymerization, interfacialpolymerization, coacervation or altogether (all of said techniques havebeen described in the prior art), optionally in the presence of apolymeric stabilizer or of a cationic copolymer.

Resins may be produced by the polycondensation of an aldehyde (e.g.formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid orglycolaldehyde and mixtures thereof) with an amine such as urea,benzoguanamine, glycoluryl, melamine, methylol melamine, methylatedmethylol melamine, guanazole and the like, as well as mixtures thereof.Alternatively one may use preformed resins alkylolated polyamines suchas those commercially available under the trademark Urac© (origin: CytecTechnology Corp.), Cy mel® (origin: Cytec Technology Corp.), Urecoll® orLuracoll® (origin: BASF).

Others resins one are the ones produced by the polycondensation of an apolyol, like glycerol, and a polyisocyanate, like a trimer ofhexamethylene diisocyanate, a trimer of isophorone diisocyanate orxylylene diisocyanate or a Biuret of hexamethylene diisocyanate or atrimer of xylylene diisocyanate with trimethylolpropane (known with thetradename of Takenate®, origin: Mitsui Chemicals), among which a trimerof xylylene diisocyanate with trimethylolpropane and a Biuret ofhexamethylene diisocyanate.

Some of the seminal literature related to the encapsulation of perfumesby polycondensation of amino resins, namely melamine based resins withaldehydes includes represented by articles such as those published by K.Dietrich et al. Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683,as well as 1990, vol. 41, page 91. Such articles already describe thevarious parameters affecting the preparation of such core-shellmicrocapsules following prior art methods that are also further detailedand exemplified in the patent literature. U.S. Pat. No. 4,396,670, tothe Wiggins Teape Group Limited is a pertinent early example of thelatter. Since then, many other authors have enriched the literature inthis field and it would be impossible to cover all publisheddevelopments here, but the general knowledge in encapsulation technologyis very significant. More recent publications of pertinency, whichdisclose suitable uses of such microcapsules, are represented forexample by the article of H. Y. Lee et al. Journal ofMicroencapsulation, 2002, vol. 19, pages 559-569, international patentpublication WO 01/41915 or yet the article of S. Bône et al. Chimia,2011, vol. 65, pages 177-181.

By “perfumery base” what is meant here is a composition comprising atleast one perfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I). Moreover, by“perfuming co-ingredient” it is meant here a compound, which is used ina perfuming preparation or a composition to impart a hedonic effect. Inother words such a co-ingredient, to be considered as being a perfumingone, must be recognized by a person skilled in the art as being able toimpart or modify in a positive or pleasant way the odor of acomposition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the intended use orapplication and the desired organoleptic effect. In general terms, theseperfuming co-ingredients belong to chemical classes as varied asalcohols, lactones, aldehydes, ketones, esters, ethers, acetates,nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compoundsand essential oils, and said perfuming co-ingredients can be of naturalor synthetic origin.

In particular one may cite perfuming co-ingredients knows for having asimilar olfactive note, such as: In particular one may cite perfumingco-ingredients which are commonly used in perfume formulations, such as:

-   -   Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal,        10-undecenal, octanal and/or nonenal;    -   Aromatic-herbal ingredients: eucalyptus oil, camphor,        eucalyptol, menthol and/or alpha-pinene;    -   Balsamic ingredients: coumarine, ethylvanillin and/or vanillin;    -   Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl        acetate, citronellyl nitrile, orange terpenes, limonene,        1-P-menthen-8-yl acetate and/or 1,4(8)-P-menthadiene;    -   Floral ingredients:Methyl dihydrojasmonate, linalool,        citronellol, phenylethanol,        3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde,        benzyl acetate, benzyl salicylate,        tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta ionone,        methyl 2-(methylamino)benzoate,        (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one,        hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol,        3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate,        geraniol, P-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyle        acetate, 1,1-dimethyl-2-phenylethyl acetate,        4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis        methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, verdyl        proprionate, geranyl acetate, tetrahydro linalool,        cis-7-P-methanol, Propyl (S)-2-(1,1-dimethylpropoxy)propanoate,        2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate,        4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde,        amylcinnamic aldehyde, 4-phenyl-2-butanone, isononyle acetate,        4-(1,1-diméthyléthyl)-1-cyclohexyl acetate, verdyl isobutyrate        and/or mixture of methyliononesisomers;    -   Fruity ingredients: gamma undecalactone, 4-decanolide, ethyl        2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate,        gamma nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate,        ethyl 2-methyl-1,3-dioxolane-2-acetate and/or diethyl        1,4-cyclohexanedicarboxylate;    -   Green ingredients: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde,        2-tert-butyl-1-cyclohexyl acetate, styrallyl acetate, allyl        (2-methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether,        (Z)-3-hexen-1-ol and/or        1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;    -   Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione,        pentadecenolide, 3-methyl-5-cyclopentadecen-1-one,        1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-g-2-benzopyrane,        (1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropyl        propanoate, pentadecanolide and/or        (1S,1′R)-[1-(3′,3′-Dimethyl-1′-cyclohexyl)ethoxycarbonyl]methyl        propanoate;    -   Woody ingredients:        1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1-ethanone,        patchouli oil, terpenes fractions of patchouli oil,        (1′R,E)-2-ethyl-4-(2′,2′,3′-trimethyl-3′-cyclopenten-1′-yl)-2-buten-1-ol,        2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,        Methyl cedryl ketone,        5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol,        1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one        and/or isobornyl acetate;    -   Other ingredients (e.g. amber, powdery spicy or watery):        dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of        its stereoisomers, heliotropin, anisic aldehyde, eugenol,        cinnamic aldehyde, clove oil,        3-(1,3-benzodioxol-5-yl)-2-methylpropanal and/or        3-(3-isopropyl-1-phenyl)butanal.

A perfumery base according to the invention may not be limited to theabove mentioned perfuming co-ingredients, and many other of theseco-ingredients are in any case listed in reference texts such as thebook by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair,N.J., USA, or its more recent versions, or in other works of a similarnature, as well as in the abundant patent literature in the field ofperfumery. It is also understood that said co-ingredients may also becompounds known to release in a controlled manner various types ofperfuming compounds.

By “perfumery adjuvant” we mean here an ingredient capable of impartingadditional added benefit such as a color, a particular light resistance,chemical stability, etc. A detailed description of the nature and typeof adjuvant commonly used in perfuming composition cannot be exhaustive,but it has to be mentioned that said ingredients are well known to aperson skilled in the art. One may cite as specific non-limitingexamples the following: viscosity agents (e.g. surfactants, thickeners,gelling and/or rheology modifiers), stabilizing agents (e.g.preservatives, antioxidant, heat/light and or buffers or chelatingagents, such as BHT), coloring agents (e.g. dyes and/or pigments),preservatives (e.g. antibacterial or antimicrobial or antifungal or antiirritant agents), abrasives, skin cooling agents, fixatives, insectrepellants, ointments, vitamins and mixtures thereof.

It is understood that a person skilled in the art is perfectly able todesign optimal formulations for the desired effect by admixing the abovementioned components of a perfuming composition, simply by applying thestandard knowledge of the art as well as by trial and errormethodologies.

An invention's composition consisting of at least one compound offormula (I) and at least one perfumery carrier consists of a particularembodiment of the invention as well as a perfuming compositioncomprising at least one compound of formula (I), at least one perfumerycarrier, at least one perfumery base, and optionally at least oneperfumery adjuvant.

According to a particular embodiment, the compositions mentioned above,comprise more than one compound of formula (I) and enable the perfumerto prepare accords or perfumes possessing the odor tonality of variouscompounds of the invention, creating thus new building block forcreation purposes.

For the sake of clarity, it is also understood that any mixtureresulting directly from a chemical synthesis, e.g. a reaction mediumwithout an adequate purification, in which the compound of the inventionwould be involved as a starting, intermediate or end-product could notbe considered as a perfuming composition according to the invention asfar as said mixture does not provide the inventive compound in asuitable form for perfumery. Thus, unpurified reaction mixtures aregenerally excluded from the present invention unless otherwisespecified.

The invention's compound can also be advantageously used in all thefields of modern perfumery, i.e. fine or functional perfumery, topositively impart or modify the odor of a consumer product into whichsaid compound (I) is added. Consequently, another object of the presentinvention consists of by a perfumed consumer product comprising, as aperfuming ingredient, at least one compound of formula (I), as definedabove.

The invention's compound can be added as such or as part of aninvention's perfuming composition.

For the sake of clarity, “perfumed consumer product” is meant todesignate a consumer product which delivers at least a pleasantperfuming effect to the surface or space to which it is applied (e.g.skin, hair, textile, or home surface). In other words, a perfumedconsumer product according to the invention is a perfumed consumerproduct which comprises a functional formulation, as well as optionallyadditional benefit agents, corresponding to the desired consumerproduct, and an olfactive effective amount of at least one invention'scompound. For the sake of clarity, said perfumed consumer product is anon-edible product.

The nature and type of the constituents of the perfumed consumer productdo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the nature and thedesired effect of said product.

Non-limiting examples of suitable perfumed consumer product include aperfume, such as a fine perfume, a splash or eau de parfum, a cologne ora shave or after-shave lotion; a fabric care product, such as a liquidor solid detergent, a fabric softener, a liquid or solid scent booster,a fabric refresher, an ironing water, a paper, a bleach, a carpetcleaner, a curtain-care product; a body-care product, such as a haircare product (e.g. a shampoo, a coloring preparation or a hair spray, acolor-care product, a hair shaping product, a dental care product), adisinfectant, an intimate care product; a cosmetic preparation (e.g. askin cream or lotion, a vanishing cream or a deodorant or antiperspirant(e.g. a spray or roll on), a hair remover, a tanning or sun or after sunproduct, a nail product, a skin cleansing, a makeup); or a skin-careproduct (e.g. a soap, a shower or bath mousse, oil or gel, or a hygieneproduct or a foot/hand care products); an air care product, such as anair freshener or a “ready to use” powdered air freshener which can beused in the home space (rooms, refrigerators, cupboards, shoes or car)and/or in a public space (halls, hotels, malls, etc.); or a home careproduct, such as a mold remover, a furnisher care product, a wipe, adish detergent or a hard-surface (e.g. a floor, bath, sanitary or awindow-cleaning) detergent; a leather care product; a car care product,such as a polish, a wax or a plastic cleaner.

Some of the above-mentioned perfumed consumer products may represent anaggressive medium for the invention's compounds, so that it may benecessary to protect the latter from premature decomposition, forexample by encapsulation or by chemically binding it to another chemicalwhich is suitable to release the invention's ingredient upon a suitableexternal stimulus, such as an enzyme, light, heat or a change of pH.

The proportions in which the compounds according to the invention can beincorporated into the various aforementioned products or compositionsvary within a wide range of values. These values are dependent on thenature of the article to be perfumed and on the desired organolepticeffect as well as on the nature of the co-ingredients in a given basewhen the compounds according to the invention are mixed with perfumingco-ingredients, solvents or additives commonly used in the art.

For example, in the case of perfuming compositions, typicalconcentrations are in the order of 0.001% to 50% by weight, or evenmore, of the compounds of the invention based on the weight of thecomposition into which they are incorporated. In the case of perfumedconsumer product, typical concentrations are in the order of 0.1% to 20%by weight, or even more, of the compounds of the invention based on theweight of the consumer product into which they are incorporated.

EXAMPLES

The invention will now be described in further detail by way of thefollowing examples, wherein the abbreviations have the usual meaning inthe art, the temperatures are indicated in degrees centigrade (° C.);NMR spectra were acquired using either a Bruker Avance II Ultrashield400 plus operating at 400 MHz, (¹H) and 100 MHz (¹³C) or a Bruker AvanceIII 500 operating at 500 MHz (¹H) and 125 MHz (¹³C) or a Bruker AvanceIII 600 cryoprobe operating at 600 MHz (¹H) and 150 MHz (¹³C), thechemical shifts δ are indicated in ppm with respect to TMS as standard,the coupling constants J are expressed in Hz.

Example 1 Synthesis of Compounds of Formula (I)—Preparation of a Mixtureof1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-(4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-onea) Preparation of a mixture of4a,7,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one and4a,5,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one

A solution of 2,3,6-trimethylcyclohexanone (108 g, 0.77 mol) andtoluenesulfonic acid (2.0 g, 11 mmol) in cyclohexane (200 mL) was warmedto 70° C. and methyl vinyl ketone (54 g, 0.77 mol) was added slowlydropwise. The mixture was heated at 70° C. for a further 15 hours thencooled and treated with 10% NaOH solution. The aqueous phase wasre-extracted with diethyl ether, the combined organic phase was washedwith brine then dried over Na₂SO₄ and filtered and the solvents removedin vacuo to yield as a mixture of cyclized and non-cyclized diketonewhich was used directly in the next cyclization step 124 g.

2,5,6-trimethyl-2-(3-oxobutyl)cyclohexan-1-one (non-cyclized diketone)

¹H (CDCl₃, 500 MHz): δ 0.97 (s, 3H), 0.99 (d, J 6.5, 3H), 1.04 (d, J6.2, 3H), 1.36-1.47 (m, 1H), 1.51-1.75 (m, 4H), 1.82 (dt, J 13.6, 3.3,1H), 2.03-2.12 (m, 1H), 1.78-1.85 (m, 1H), 1.89 (td, J 14.0, 4.5, 1H),2.08 (tt, J 13.8, 4.1, 1H), 2.27 (bq, J 7.5, 1H), 2.33-2.38 (m, 1H),2.56 (ddd, J 17.6, 15, 5.1, 1H), 5.77 (s, 1H) ppm.

13C 99620

¹³C (CDCl₃, 125 MHz): δ 12.0 (q), 20.8 (q), 22.4 (q), 30.0 (t)), 30.1(q), 30.9 (t), 38.2 (t), 39.3 (t), 41.4 (d), 47.0 (s), 47.7 (d), 208.1(s), 218.4 (s) ppm.

A solution of a mixture of diketone and enones obtained above (mixtureof isomers, 104 g, 0.495 mol) and KOH (8.0 g, 142 mmol) in EtOH (35 mL)was heated at 70° C. for 35 hours then cooled. Diluted with ether, theorganic phase was washed with sodium bicarbonate then dried over MgSO₄and concentrated in vacuo to yield the crude enone as a complex mixtureof isomers, 60 g, 63%. The mixture was purified by Leybold (continuouswiped film) distillation (145° C. vide 0.3 mbar) to give the enone as amixture of(4aSR,7SR,8RS)-4a,5,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one,(4aSR,8SR)-4a,7,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-oneand(4aSR,8RS)-4a,5,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-onein a respective amount of 8%, 82% and 10%.

Minor isomer:(4aSR,7SR,8RS)-4a,7,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one

¹H (CDCl₃, 500 MHz): δ 0.94 (d, J 7.4, 3H), 1.25 (d, J 7.4, 3H), 1.31(s, 3H), 1.31-1.35 (m, 1H), 1.44 (dt, J 13.8, 3.8, 1H), 1.58 (td, J13.7, 4.1, 1H), 1.69, (ddd, J 13.1, 5.0, 2.4, 1H), 1.78-1.85 (m, 1H),1.89 (td, J 14.0, 4.5, 1H), 2.08 (tt, J 13.8, 4.1, 1H), 2.27 (bq, J 7.5,1H), 2.33-2.38 (m, 1H), 2.56 (ddd, J 17.6, 15, 5.1, 1H), 5.77 (s, 1H)ppm.

¹³C (CDCl₃, 125 MHz): δ 20.0 (q), 22.9 (q), 23.2 (t), 25.3 (q), 34.3(t), 34.4 (d), 34.7 (t), 35.5 (s), 40.3 (t), 45.2 (d), 127.2 (d), 174.3(s), 199.8 (s) ppm.

Major isomer:(4aSR,8SR)-4a,7,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one

¹³C (CDCl₃, 125 MHz): δ 12.5, 14.7, 15.9, 21.2, 23.2, 23.4 (q), 29.0,30.9, 33.6, 33.9 (t), 36.1 (d), 36.1 (t), 36.1, 36.3 (s), 37.7 (d),38.3, 38.5 (t), 40.3, 40.6 (d), 41.0 (t), 121.9, 123.9 (d), 172.6, 173.8(s), 198.8, 200.4 (s) ppm.

b) Preparation of a mixture of4a,7,8-trimethyloctahydronaphthalen-2(1H)-one and4a,5,8-trimethyloctahydronaphthalen-2(1H)-one

Palladized charcoal (5%, Pd/C, 1.42 g) was added to a solution of theenone mixture 25 obtained in step a) (57 g, 296 mmol) in ethyl acetate(80 mL) and the suspension evacuated in vacuo then purged with hydrogengas (3×) then stirred under an atmosphere of hydrogen gas (2 bar) for 24hours. The suspension was filtered and washed with ethyl acetate, thenthe solvents removed in vacuo and the residue further purified by bulbto bulb (Kügelrohr) distillation 150° C. at 0.5 mbar and gave thesaturated ketone as a complex mixture of isomers; 60 g, 99%.

Major isomers are:

(4aSR,7RS,8SR,8aRS)-4a,7,8-trimethyloctahydronaphthalen-2(1H)-one

¹H (CDCl₃, 500 MHz): δ 0.82, (d, J 6.1, 3H), 0.94 (d, J 5.4, 3H), 1.03(s, 3H), 1.19 (td, J 13.8, 4.1, 1H), 1.16-1.24 (m, 1H), 1.30-1.39 (m,1H), 1.45 (td, J 13.6, 5.1, 1H), 1.50-1.56 (m, 2H), 1.68 (ddd, J 13.6,6.7, 1.9, 1H), 1.98 (t, J 14.4, 1H), 2.28 (ddt, J 15.7, 4.6, 2.3, 1H),2.44 (dd, J 14.7, 6.7, 1H), 2.50 (ddd, J 15.0, 4.1, 2.1, 1H) ppm.

¹³C (CDCl₃, 125 MHz): δ 16.0 (q), 16.1 (q), 20.5 (q), 30.7 (t), 33.3(s), 37.7 (t), 38.8 (d), 39.0 (d), 40.4 (t), 40.9 (t), 41.8 (t), 50.2(d), 212.4 (s) ppm.

(4aSR,8SR,8aSR)-4a,7,8-trimethyloctahydronaphthalen-2(1H)-one

¹H (CDCl₃, 500 MHz): δ 0.78 (d, J 7.4, 3H), 0.89 (d, J 6.9, 3H), 1.42(s, 3H), 1.28-1.47 (m, 4H), 1.60-1.70 (m, 2H), 1.78-1.86 (m, 2H),1.98-2.06 (m, 1H), 2.22 (dd, J 15.9, 4.3, 1H), 2.34-2.43 (m, 2H), 2.60(dd, J 15.9, 6.3 (1H) ppm.

¹³C (CDCl₃, 125 MHz): δ 11.9 (q), 18.5 (q), 25.9 (t), 28.6 (q), 32.6(s), 35.4 (t), 35.5 (d), 36.6 (t), 37.5 (t), 37.9 (d), 42.7 (t), 47.0(d), 212.8 (s) ppm.

(4aSR,7SR,8SR,8aRS)-4a,7,8-trimethyloctahydronaphthalen-2(1H)-one

¹H (CDCl₃, 500 MHz): δ characteristic signals:—0.78 (d, J 6.7, 3H), 0.83(d, J 7.0, 3H), 1.05 (s, 3H).

¹³C (CDCl₃, 125 MHz): δ 12.1 (q), 15.7 (q), 17.2 (q), 28.6 (t), 33.7(s), 33.9 (d), 34.4 (d), 34.8 (t), 38.1 (t) 41.0 (t), 41.3 (t), 43.4(d), 212.5 (s) ppm.

c) Preparation of a mixture of2-ethynyl-4a,7,8-trimethyldecahydronaphthalen-2-ol and2-ethynyl-4a,5,8-trimethyldecahydronaphthalen-2-ol

A solution of the cis and trans decalone obtained in the previous step(26.7 g, 137 mmol) in THF (11 mL) was added slowly dropwise to a stirredsolution of ethynyl magnesium bromide (0.5 M in THF, 385 mL, 192 mmol)cooled to 4° C. in an ice bath. The solution was allowed to warm toambient temperature and stirred overnight. The reaction mixture waspoured into ice and extracted with diethyl ether, the organic phasewashed with saturated NH₄Cl solution, then brine, dried over Na₂SO₄,filtered and the solvents removed in vacuo to yield the crudepropargylic alcohol as a complex mixture of isomers, 26.0 g as a brownoil. The complex mixture of isomeric alcohols was used without furtherpurification in the next step.

d) Preparation of a mixture of1-(4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-(4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one

The mixture of propargylic alcohols (19.0 g, 86 mmol) was dissolved informic acid (55 mL, 90%) and heated at 80° C. for 2 hours then cooledand poured into a mixture of ice and water. The aqueous phase wasextracted with pentane, the organic phase washed with water, thensaturated NaHCO₃ solution, brine, dried over Na₂SO₄, filtered and thesolvents removed in vacuo to yield the crude enone as a complex mixtureof isomers, 20.0 g. Further purification by vacuum distillation with aVigreux column, 0.2 mbar, b.p. 65-90° C., gave the enone as a mixture ofisomers comprising1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-(4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-(4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,9.8 g, 50% yield.

Small quantities of some individual isomers were isolated to yield

1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one

¹H (CDCl₃, 500 MHz): δ 0.85 (s, 3H), 0.90-1.05 (m, 4H), 1.12 (q, J 12.8,1H), 1.34 (td, J 12.6, 3.9, 1H), 1.41-1.54 (m, 1H), 1.55 (s, 3H), 1.62(s, 3H), 1.58-1.70 (m, 4H), 1.94-2.07 (m, 4H), 2.13 (s, 3H), 2.30 (tt, J12.2, 3.4, 1H) ppm.

¹³C (CDCl₃, 125 MHz): δ 18.5 (q), 18.8 (q), 24.0 (t), 26.8 (q), 26.9(t), 27.9 (q), 29.4, 31.2 (t), 31.6 (s), 39.8 (t), 48.4, 52.1 (d),124.1, 127.7 (s), 212.2 (s) ppm.

1-((4aSR,8SR,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one

¹H (CDCl₃, 500 MHz): δ 0.87 (d, J 6.4, 3H), 0.85-0.89 (m, 2H), 1.03 (s,3H), 1.06 (d, J 7.0, 3H), 1.22 (td, J 12.8, 3.9, 1H), 1.35-1.47 (m, 4H),1.51 (ddd, J 12.9, 6.3, 1.3, 1H), 1.63-1.73 (m, 2H), 1.96-2.00 (m, 1H),2.09-2.18 (m, 1H), 2.29 (s, 3H), 6.85 (bs, 1H) ppm.

¹³C (CDCl₃, 125 MHz): δ 19.8 (q), 20.2 (q), 20.3 (t), 25.4 (q), 26.4(q), 30.0 (t), 31.3 (t), 32.1 (s), 34.8 (d), 36.3 (d), 36.4 (t), 48.9(d), 139.2 (s), 140.8 (d), 199.4 (s) ppm.

Example 2 Synthesis of Compounds of Formula (I)—Preparation of a Mixtureof1-((4aSR,8SR,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-((4aSR,8SR,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-onea) Preparation of(4aRS,8RS,8aRS)-2-ethynyl-4a,7,8-trimethyldecahydronaphthalen-2-ol

A solution of ethynyl magnesium chloride (10.7 mL, 0.5 M, 5.35 mmol) wasadded to a solution of(4aSR,8SR,8aRS)-4a,7,8-trimethyloctahydronaphthalen-2(1H)-one (isolatedfrom example 1 step b), 800 mg, 4.12 mol) in THF (2 mL) cooled to 0° C.After warming to ambient temperature and stirring for a further 2 hrsthe reaction was poured into a mixture of ice and saturated NH₄Cl, andextracted with ether. The organic phase was washed with brine and driedover Na₂SO₄, filtered and the solvents removed in vacuo to yield thecrude alcohol, 800 mg, which was used without further purification inthe next step.

¹H (CDCl₃, 500 MHz): δ 0.83 (s, 3H), 0.85 (d, J 6.1, 3H), 0.92 (d, J6.4, 3H), 0.94-1.07 (m, 5H), 1.13 (ddd, J 13.0, 10.2, 2.7, 1H), 1.19(dd, J 12.8, 4.2, 1H), 1.24-1-52 (m, 5H), 1.75 (td, J 12.7, 4.7, 1H),1.80-1.87 (m, 1H), 2.02 (dt, J 12.3, 2.5, 1H), 2.21 (bs, 1H), 2.47 (s,1H) ppm.

13C:111630

¹³C (CDCl₃, 125 MHz): δ 16.4 (q), 16.6 (q), 20.8 (q), 30.8 (t), 33.2(s), 35.3 (t), 37.5 8d), 38.6 (t), 39.2 (t), 40.9 (t), 47.9 (d), 70.6(s), 72.1 (s), 87.8 (s) ppm.

b) Preparation of a mixture of1-((4aSR,8SR,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-((4aSR,8SR,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one

Conditions reported in example 1 d) were applied to(4aRS,8RS,8aRS)-2-ethynyl-4a,7,8-trimethyldecahydronaphthalen-2-olproviding a mixture of1-((4aSR,8SR,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-((4aSR,8SR,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one.

Major isomer:1-((4aSR,8SR,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one.

¹H (CDCl₃, 500 MHz): δ 0.75 (s, 3H), 0.93 (d, J 6.2, 3H), 0.78-0.93 (m,4H), 1.07-1.62 (m, H), 2.01 (bm, 1H), 2.29 (s, 3H), 2.61 (dd, J 18, 3.5,1H), 6.81 (bm, 1H) ppm.

¹³C (CDCl₃, 125 MHz): δ 16.3 (q), 17.5 (q), 20.7 (q), 25.3 (t), 30.8(t), 39.1 (d), 39.4 (d), 40.8 (t), 43.5 (t), 45.6 (d), 139.2 (s), 141.7(d), 199.4 (s) ppm.

Example 3 Synthesis of Compounds of Formula (I)—Preparation of a Mixtureof1-((4aSR,7RS)-4a,7,8-trimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)ethan-1-onea) Preparation of(4aSR,8SR)-4a,7,8-trimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one

A solution of the enone mixture obtained in a previous step (20.0 g, 104mmol) in THF (25 mL) was added slowly dropwise to a stirred solution ofethynyl magnesium bromide (0.5 M in THF, 354 mL, 177 mmol) cooled to 4°C. in an ice bath. The solution was allowed to warm to ambienttemperature and stirred overnight. The reaction mixture was poured intoa mixture of ice/saturated NH₄Cl solution and extracted with diethylether, the organic phase washed with saturated NH₄Cl solution, thenbrine, dried over Na₂SO₄, filtered and the solvents removed in vacuo toyield the crude propargylic alcohol as a complex mixture of isomers,20.0 g as a brown oil. The complex mixture of isomeric alcohols was usedwithout further purification in the next step.

b) Preparation of1-((4aSR,7RS)-4a,7,8-trimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)ethan-1-one

A solution of the propargylic alcohol mixture (20.0 g, 92 mmol) in ethylacetate (50 mL) was treated with Amberlyst A-15 (10.0 g) and thesuspension heated under reflux for 4 hours then cooled and filteredthrough a small plug of silica (3 cm) and washed with ethyl acetate. Thecombined organic phase was washed with saturated sodium bicarbonatesolution, then brine, dried over Na₂SO₄, filtered and the solventsremoved in vacuo to yield the crude dienone as a mixture of isomers87:13. Further purification by Fischer distillation 0.15 mbar b.p 70-85°C. gave the pure dienone as a mixture of isomers (87:13), 12.8 g, 64%.

Major isomer:1-((4aSR,7RS)-4a,7,8-trimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)ethan-1-one

¹H (CDCl₃, 500 MHz): δ 0.91 (s, 3H), 1.00 (d, J 7.0, 3H), 1.08 (d, J7.2, 3H), 1.27 (tt, J 12.3, 5.4, 1H), 1.31-1.57 (m, 3H), 1.60 (ddd, J13, 5.9, 1.3, 1H), 1.88 (s, 3H), 2.15-2.30 (m, 2H), 2.35 (d, J 1.6, 3H),2.49 (dt, J 19, 4.6, 1H), 7.43 (d, J 1.6, 1H) ppm.

Example 4

Preparation of a Perfuming Composition

A perfuming composition, of the woody type, was prepared by admixing thefollowing ingredients:

Parts by weight Ingredient 200 Ambrox ®¹⁾ 400 Bergamot oil 40 10%*7-Methy1-2H,4H-1,5-benzodioxepin-3-one 20 Cardamon oil 600 Lemon oil 100Coumarin 20 Alpha damascone 200(1′R,E)-2-ethy1-4-(2′,2′,3′-trimethyl-3′-cyclopenten-1′-yl)-2-buten-1-ol 1000 Dihydromyrcenol 200(1-Ethoxyethoxy)cyclododecane 200 Hedione ®²⁾ HC 2003-(1,3-Benzodioxol-5-yl)-2-methylpropanal 200 Helvetolide ®³⁾ 200Iralia ®⁴⁾ Total 20 Nutmeg oil 2000 Hedione ®⁵⁾ 10 Neobutenone ®⁶⁾ Alpha20 Pink pepper oil 100 Nirvanol ®⁷⁾ 100 (Z)-3-Hexen-1-ol salicylate 102-Ethyl-4,4-dimethylcyclohexanone 60 Vetiver oil 100(+)-8,13:13,20-Diepoxy-15,16-dinorlabdane 6000¹⁾(−)-(8R)-8,12-epoxy-13,14,15,16-tetranorlabdane^(a)) ²⁾high cis methyldihydrojasmonate^(a))³⁾(1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropylpropanoate^(a)) ⁴⁾mixture of methylionones isomers^(a)) ⁵⁾methyldihydrojasmonate^(a))⁶⁾1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one^(a))⁷⁾3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol^(a))*in dipropyleneglycol ^(a))origin: Firmenich SA, Geneva, Switzerland

The addition of 4000 parts by weight of compound as obtained in Example1 to the above-described composition imparted to the latter a reinforcedrooty/powdery, ambery and smoky characters by blending very well withwoody-vetiver (Vetiver oil), amber (Ambrox©) and powdery-violet (Iralia®Total) elements present in the original formula. Moreover, thisingredient twists this formula in a more masculine direction. Saidcompound is the most powerful in bottom and top note.

When instead of compound as obtained in Example 1 was added the sameamount of a mixture of1-((4aRS,8RS,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,8RS,8aRS)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,8RS,8aSR)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand1-((4aRS,8RS,8aRS)-4a,8-dimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one(20:12:39:28), then said ingredient provided a similar effect to the oneof Example 1 with the lighter powdery character. This ingredient is lesspowerful and more unisex so more versatile.

When instead of compound as obtained in Example 1 was added the sameamount of prior art's1-[(4aRS,8SR,8aSR)-4a,8-dimethyl-3,4,4a,5,6,7,8,8a-octahydro-2-naphthalenyl]ethanone,then this ingredient pushed the fruity-Dasmascone (Damascone Alpha)element (an element not observed with the invention's compounds) andtwists the woody accord in a more cedar like direction. This ingredientis the less powerful.

1. A method of using a perfuming ingredient of a compound of formula

in a form of any one of its stereoisomers or a mixture thereof, whereindotted lines represent a carbon-carbon single bond or a carbon-carbon adouble bond; and one R¹ group represents a hydrogen atom and a second R¹group represents a methyl group.
 2. The method according to claim 1,characterized in that the two methyl groups at carbon 4a and 8 are in ananti-configuration.
 3. The method according to claim 1, characterized inthat the compound of formula (I) is a compound of formula

in a form of any one of its stereoisomers or a mixture thereof, andwherein at least one dotted line represents a carbon-carbon single bondand the others a carbon-carbon double bond; and one R¹ group representsa hydrogen atom and a second R¹ group represents a methyl group.
 4. Themethod according to claim 3, characterized in that the compound offormula (I) is a compound of formula

in a form of any one of its stereoisomers or a mixture thereof.
 5. Themethod according to claim 1, characterized in that the compound offormula (I) is a compound of formula

in a form of any one of its stereoisomers or a mixture thereof, andwherein one dotted line represents a carbon-carbon single bond and theother a carbon-carbon double bond; and one R group represents a hydrogenatom and a second R¹ group represents a methyl group.
 6. The methodaccording to claim 5, characterized in that the compound of formula (I)is a compound of formula

in a form of any one of its stereoisomers or a mixture thereof, whereinbold and hatched lines indicate a relative or absolute configuration;dotted lines represent a carbon-carbon single bond or a carbon-carbondouble bond; and one R¹ group represents a hydrogen atom and a second R¹group represents a methyl group.
 7. The method according to claim 5,characterized in that it is a compound of formula (I) is a compound offormula

in a form of any one of its stereoisomers or a mixture thereof, whereinbold and hatched lines indicate a relative or absolute configuration;and dotted lines represent a carbon-carbon single bond or acarbon-carbon double bond.
 8. The method according to claim 5,characterized in that it is a compound of formula (I) is a compound offormula

in a form of any one of its stereoisomers or a mixture thereof, whereinbold and hatched lines indicate a relative or absolute configuration;and dotted lines represent a carbon-carbon single bond or acarbon-carbon double bond.
 9. The method according to claim 1,characterized in that the compound of formula (I) is1-((4aRS,8aRS)-4a,7,8-trimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aSR)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7RS,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aRS,7SR,8RS,8aRS)-4a,7,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aSR)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5SR,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one,1-((4aSR,5RS,8RS,8aRS)-4a,5,8-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-oneand/or mixtures thereof.
 10. A compound of formula (I) as defined inclaim
 1. 11. A perfuming composition comprising i) at least one compoundof formula (I), as defined in claim 10; ii) at least one ingredientselected from the group consisting of a perfumery carrier and aperfumery base; and iii) optionally at least one perfumery adjuvant. 12.A perfumed consumer product comprising at least one compound of formula(I), as defined in claim
 10. 13. The perfumed consumer product accordingto claim 12, characterized in that the perfumed consumer product is aperfume, a fabric care product, a body-care product, a cosmeticpreparation, a skin-care product, an air care product or a home careproduct.
 14. The perfumed consumer product according to claim 13,characterized in that the perfumed consumer product is a fine perfume, asplash or eau de perfume, a cologne, an shave or after-shave lotion, aliquid or solid detergent, a fabric softener, a fabric refresher, anironing water, a paper, a bleach, a carpet cleaners, curtain-careproducts a shampoo, a coloring preparation, a color care product, a hairshaping product, a dental care product, a disinfectant, an intimate careproduct, a hair spray, a vanishing cream, a deodorant or antiperspirant,hair remover, tanning or sun product, nail products, skin cleansing, amakeup, a perfumed soap, shower or bath mousse, oil or gel, or afoot/hand care products, a hygiene product, an air freshener, a “readyto use” powdered air freshener, a mold remover, furnisher care, wipe, adish detergent or hard-surface detergent, a leather care product, a carcare product.
 15. A method to confer, enhance, improve or modify odorproperties of a perfuming composition or of a perfumed article, whichmethod comprises adding to said composition or article an effectiveamount of at least a compound of formula (I) as defined in claim 10.